JP2007292981A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which can provide a stable image even in long-term duration, is excellent in anti-electrostatic offset characteristic in a low-humidity environment, and is excellent in storage stability even in a high-temperature and high-humidity environment. <P>SOLUTION: The toner contains at least a binder resin, a colorant, and a layered compound having Al and Si, wherein the toner is created by subjecting the binder resin, the colorant and the layered compound to at least a raw material mixing step, a melt kneading step, a pulverizing step, and a classifying step, the standard deviation of the arithmetic mean diameter of the layered compound prior to the raw material mixing step is ≤2.0, and the content of the particles having a median diameter of ≤4 μm and ≥10 μm is ≤3%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used for electrophotography, electrostatic recording, electrostatic printing, and toner jet recording.

  Conventionally, a number of methods are known as electrophotographic methods. Generally, a photoconductive material is used to form an electric latent image on a photoreceptor, and toner is applied to a transfer material such as paper as necessary. There is known a method for obtaining a toner image by transferring an image and fixing the image by heat, pressure, or the like.

  Various methods and apparatuses have been developed as a fixing method, but the most common method at present is a pressure heating method using a heated roller, film or belt. In particular, pressure heating using a film is widely used because it can be fixed with a relatively low amount of heat.

  In recent years, copying apparatuses and printers using electrophotography have been required to have higher speed and higher image quality, and the process speed of the apparatus has to be accelerated while providing high-definition images. However, as the speed increases, the load on the toner increases, and the time for the toner to obtain a charge is shortened. Therefore, the image density is likely to decrease due to toner wear and unstable charging. In particular, when fixing is performed at high speed and continuously in an environment where the chargeability of the toner is likely to increase, such as under low humidity, a phenomenon called electrostatic offset in which the toner adheres to the fixing roller is likely to occur. In addition, as the speed increases, the temperature rises particularly in a high temperature environment, and the toner tends to aggregate due to surface alteration and the like, particularly in a high temperature and high humidity environment.

  A toner capable of preventing these phenomena as much as possible is indispensable for high speed and high stability, and improvement is desired.

  In Patent Documents 1 to 3, an attempt is made to improve charging stability by using an azo organic pigment. However, sufficient performance has not been obtained with respect to electrostatic offset resistance. In Patent Document 3, an attempt is made to improve charge stability and scattering from the initial durability to the end by using an azo organic pigment and a quaternary ammonium salt as a charge control agent. However, there is room for improvement in resistance to electrostatic offset.

  In Patent Document 4, an attempt is made to improve toner scattering and charge rising characteristics by using organic bentonite with respect to a polyester resin. However, further improvements in electrostatic offset and wear resistance are desired. Patent Document 5 attempts to improve toner scattering and charging stability by using organic bentonite, but there is still room for improvement in electrostatic offset. In Patent Documents 6 to 8, attempts are made to improve charging stability by dispersing a charge control agent prepared from a quaternary ammonium salt and a specific inorganic pigment in a resin. However, improvement in electrostatic offset resistance is required. In Patent Document 9, an attempt is made to improve charging stability by using organic bentonite. However, the electrostatic offset resistance and storage stability are not sufficient. In Patent Documents 10 and 11, attempts are made to obtain stable chargeability by combining a biodegradable resin and organic bentonite, but improvements are required for electrostatic offset resistance and storage stability. In Patent Document 12, attempts are made to improve stable charging performance and start-up performance by a combination of a quaternary ammonium salt and kaolin clay, talc or bentonite. However, improvement in electrostatic offset resistance and storage stability is required. ing.

JP 2003-195567 A JP 2003-215848 A JP 2003-223018 A Japanese Patent Laid-Open No. 2004-004207 JP 2004-012581 A Japanese Patent Registration No.3262892 JP-A-6-59518 JP-A-6-301241 Japanese Patent Laid-Open No. 2004-117651 JP 2004-151316 A JP 2004-151457 A JP-A-8-6295

  An object of the present invention is to provide a toner that solves the above problems. Specifically, it is an object to provide a toner that can provide a stable image even in long-term durability, has excellent electrostatic offset resistance in a low-humidity environment, and has excellent storage stability even in a high-temperature and high-humidity environment. .

  The inventors have mixed a layered compound having Al and Si and having a specific particle size distribution together with a binder resin and a colorant, and converted into a toner through a melt-kneading, fine pulverization, and classification steps for a long period of time. The present inventors have found that a stable image can be provided even in durability, excellent in electrostatic offset resistance in a low-humidity environment, and excellent in storage stability in a high-temperature and high-humidity environment, and the present invention has been completed.

  In order to achieve the above object, a first invention according to the present application provides a toner comprising at least a binder resin, a colorant, and a layered compound having Al and Si, wherein the toner is at least the binder resin. The colorant and the layered compound are produced through at least a raw material mixing step, a melt-kneading step, a pulverizing step, and a classification step, and the standard deviation of the arithmetic average diameter of the layered compound before the raw material mixing step is It is 2.0 or less, the median diameter is 4 μm or less, and the content of particles of 10 μm or more is 3% or less.

  Furthermore, in order to achieve the above object, the second invention according to the present application is characterized in that the layered compound contains 0.1 to 5% by mass of Fe.

  Furthermore, in order to achieve the above object, a third invention according to the present application is characterized in that the layered compound contains an organic substance, and the organic substance is a compound containing nitrogen.

  Furthermore, in order to achieve the above object, a fourth invention according to the present application is characterized in that the layered compound contains an organic substance, and the organic substance contains a dimethyl distearyl ammonium salt.

  Furthermore, in order to achieve the above object, a fifth invention according to the present application is characterized in that the toner contains 30 to 150 parts by mass of magnetic powder with respect to 100 parts by mass of the binder resin. .

  Furthermore, in order to achieve the above object, according to a sixth invention of the present application, the binder resin contains at least a polyester resin component of 50% by mass or more, and includes a polyester resin component and a vinyl resin component. It contains a hybrid resin component that is a reaction product.

  According to the present invention, it is possible to provide a toner that can provide a stable image even in long-term durability, is excellent in electrostatic offset resistance in a low-humidity environment, and is excellent in storage stability under high temperature and high humidity.

  Hereinafter, the present invention will be described in detail.

  By studying the present inventors, a layered compound containing Si and Al is mixed with a resin and melt-kneaded so that the compound is sufficiently dispersed inside the toner and further uniformly present on the toner surface by fine pulverization. It has been found that a toner capable of providing a stable image even in long-term durability, excellent in electrostatic offset resistance under a low humidity environment, and excellent in storage stability even under high temperature and high humidity can be obtained.

  To obtain a toner that provides a uniform image density over a long period of time and does not cause electrostatic offset even in high-speed fixing and has excellent storage stability, the toner is improved in wear resistance and uniform chargeability. There is a need to reduce the low molecular weight components in it. To achieve this, the fine dispersibility of the layered compound of the present invention, which has excellent charge imparting properties, has a slightly enhanced elasticity on the toner surface, and further incorporates low molecular weight components in the toner, is controlled. It was important.

  The content of particles having a standard deviation of the arithmetic mean diameter of 2.0 or less, a median diameter of 4 μm or less, and a particle size of 10 μm or more by finely pulverizing and classifying the layered compound according to the study by the present inventors. It was found that when the toner is made into a toner by a pulverization method after being set to 3% or less, the toner is excellent in charging stability, durability, electrostatic offset resistance, and storage stability. Regarding the particle size distribution, layered compounds with fine particle size and sharp distribution have a large specific surface area, so it is easy to incorporate substances between layers, and evenly disperse low molecular weight components in the resin while improving storage stability. This is probably because of this. Further, it seems that Si and Al are finely dispersed while being cross-linked with the resin component during the kneading through the melt-kneading. Furthermore, by grinding at an appropriate temperature, the resin on the surface is weakly crosslinked, and the layered compound is uniformly present throughout the toner, thereby improving wear resistance and sharpening the charge distribution of the toner. It is assumed that electrostatic adhesion to the fixing roller is suppressed.

  Hereinafter, materials that can be used in the toner of the present invention will be described in detail.

  In the present invention, a layered compound containing Al and Si is used as the toner material. In the present invention, any material can be used as the layered compound as long as it contains Si and Al. Examples thereof include natural viscosity minerals and artificially synthesized aluminum silicate. In particular, it is preferable to use a crystalline layered compound obtained by firing silica sand containing aluminum, dissolving it in warm water, drying it, and further through a firing step. At that time, for example, when a compound containing Fe is dissolved in warm water together with silica sand, a layered compound containing Fe can be obtained.

  When the layered compound used in the present invention contains Fe, the charge stabilization performance is increased, and the content is more preferably 0.1 to 5% by mass in the layered compound. If the Fe content is less than 0.1% by mass, the chargeability will be slightly excessive, and if it exceeds 5% by mass, the chargeability will decrease. It becomes easy to do.

  As the layered compound, those having a standard deviation of the arithmetic average diameter of 2.0 or less, a median diameter of 4 μm or less, and a content of particles of 10 μm or more of 3% or less are used. The particle size of the layered compound in the present invention refers to a value determined on a volume basis. A more preferable range of the median diameter is 3.5 μm or less, and the dispersibility of the layered compound is excellent. Further, the content of particles of 10 μm or more is more preferably 2% or less, and the dispersibility of the layered compound is excellent. The standard deviation of the arithmetic average diameter is preferably 1.2 or more and 1.8 or less because the dispersibility of the layered compound is excellent, and residual monomers and volatile components are easily incorporated, and is preferably 1.2 or more and 1.6 or less. And more preferred. The content of particles of 8 μm or more is preferably 5% or less because the dispersibility of the layered compound is excellent and low molecular weight components are easily incorporated. More preferably, it is 4% or less. The particle size of the layered compound is preferably adjusted by a fine pulverization and classification process, since the toner is excellent in concentration stability in durability and electrostatic offset resistance.

  The apparatus which can be used for the grinding | pulverization and classification process of a layered compound below is illustrated.

  As a pulverizer, a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic Industry Co., Ltd.); a cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); SK Jet Oh Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Industry Co., Ltd.);

  Classifiers include: Classy, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron) Elbow Jet (manufactured by Nippon Steel & Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.); YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.).

  If the standard deviation of the arithmetic average diameter of the layered compound exceeds 2, the particle size distribution is broad, so that the dispersibility in the toner is remarkably lowered, and the effect of the present invention cannot be obtained. Even when the mode diameter exceeds 4 μm, the dispersibility of the layered compound in the toner is lowered, so that the development density in durability becomes unstable and electrostatic offset tends to occur frequently.

  The layered compound used in the present invention may contain any inorganic and organic substances between layers. The compound contained between the layers is preferably an organic compound containing nitrogen. In the case of a compound that does not contain nitrogen, the durability is liable to decrease because the charging performance is somewhat inferior. The intercalation compound is preferably selected from monostearyl ammonium salt, dimethyl distearyl ammonium salt and methyl tristearyl ammonium salt among the compounds containing nitrogen. Among them, dimethyl distearyl ammonium salt is preferable, and more preferably, 80% by mass or more and less than 100% by mass of all intercalation compounds is dimethyl distearyl ammonium salt, and methyl tristearyl ammonium salt is more than 20% by mass. The content is less than mass%. When these compounds are present between the layers, the layered compound is excellent in dispersibility, and tends to improve durability concentration stability and electrostatic offset resistance.

  Further, the weight ratio of the organic compound between the layered compound base and the interlayer is preferably 55:45 to 70:30 because the charging uniformity is excellent. This range provides a good balance between the matrix and the organic matter. A particularly preferred range for the weight ratio is 55:45 to 65:35.

  The interlayer distance of the layered compound used in the present invention before the raw material mixing step is preferably 25 to 45 mm, more preferably 30 to 40 mm. When the interlayer distance is within this range, it is considered that the layered compound easily takes in the residual monomer or volatile component in the resin between the layers, and the storage stability tends to be improved.

  In the toner of the present invention, a binder resin, a colorant, a release agent, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then heated rolls, kneaders, extruders, etc. Toner particles (toner base material) are prepared by melting and kneading using a heat kneader to make the resins compatible with each other, cooling and solidifying the melt kneaded product using a pulverizer, and carrying out strict classification with a classifier. The toner is further mixed with a fluidity improver and / or an external additive with a mixer such as a Henschel mixer, and if necessary, coarse particles are removed using a sieving device. A toner having a fluidity improver and / or an external additive on the particle surface is obtained.

  Examples of apparatuses that can be used as toner manufacturing apparatuses are listed below, but the present invention is not limited to these.

  Examples of the mixer include Henschel mixer (manufactured by Mitsui Mining); Super mixer (manufactured by Kawata); Ribocorn (manufactured by Okawara Seisakusho); Nauter mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (Manufactured by Taiheiyo Kiko Co., Ltd.); Laedige mixer (manufactured by Matsubo);

  As a kneading machine, KRC kneader (manufactured by Kurimoto Iron Works); Bus co-kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikekai Iron Works Co., Ltd.); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); kneedex (manufactured by Mitsui Mining Co., Ltd.); Banbury mixer (manufactured by Kobe Steel);

  As a pulverizer, a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic Industry Co., Ltd.); a cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); SK Jet Oh Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Industry Co., Ltd.);

  Classifiers include: Classy, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron) Elbow Jet (manufactured by Nippon Steel & Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.); YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.).

  Furthermore, it is also preferable to use a sieving device used for sieving coarse particles and the like, and as the sieving device, Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Dalton Co.); Soniclean (Shinto Kogyo Co., Ltd.); Turbo Screener (Turbo Kogyo Co., Ltd.);

  In particular, in the present invention, it is possible to obtain a toner exhibiting desired chargeability and abrasion resistance from the above materials by setting specific conditions in the process of melt kneading and pulverizing the toner.

  In melt-kneading, it is important to adjust the heating setting of the kneader so that the resin temperature immediately after the outlet of the kneaded product is in the range of 140 to 190 ° C.

  When the resin temperature at the time of melt kneading is high and the resin temperature immediately after the discharge port exceeds 190 ° C., the dispersibility of the colorant and the layered compound is deteriorated, and the concentration is lowered and electrostatic offset is likely to occur. On the other hand, when the resin temperature is low and the resin temperature immediately after the discharge port is less than 140 ° C., the dispersibility of the layered compound deteriorates, so that the charging uniformity is inferior, and the concentration tends to decrease and electrostatic offset tends to occur.

  As the pulverizing apparatus, the pulverizing apparatus as described above can be used. However, when an airflow type pulverizer such as a jet mill is used, the toner surface is likely to be insufficiently crosslinked and wear-resistant. There is a tendency that the durability concentration is likely to decrease due to the decrease in. Therefore, it is preferable to use a mechanical pulverizer as the pulverizing means.

  The mechanical pulverization / classification system capable of optimally producing the toner of the present invention uses a powder raw material made of a coarsely pulverized product obtained by melt-kneading, cooling, and coarse pulverization in a kneading process as a first quantitative feeder. Introduced and provided with at least a rotor composed of a rotating body attached to a central rotating shaft, and a stator arranged around the rotor with a constant spacing from the rotor surface, and maintaining the spacing In a mechanical pulverizer configured so that the annular space formed by the operation is in an airtight state, a predetermined amount of the powder raw material is supplied from the first quantitative supply device to the powder inlet of the mechanical pulverizer. And the powder raw material is finely pulverized by rotating the rotor of the mechanical pulverizer at a high speed.

  The finely pulverized pulverized material is discharged from the powder discharge port of the mechanical pulverizer and introduced into the second fixed amount feeder, and a predetermined amount of finely pulverized material is fed from the second constant amount feeder into the cross airflow and the Coanda effect. Was introduced into a multi-split airflow classifier that classifies the powder into airflow, and the finely pulverized product was classified into at least fine powder, medium powder and coarse powder in the multi-split airflow classifier, and classified. In this system, a coarse powder is mixed with a powder raw material, introduced into the mechanical pulverizer, pulverized, and toner is generated from the classified medium powder.

  Here, the finely pulverized product generated in the mechanical pulverizer is discharged from the powder discharge port to the outside through the rear chamber of the mechanical pulverizer. At that time, the cooling device, the peripheral speed of the rotor, the load, or the rotor and stator are adjusted so that the room temperature T1 of the rear chamber of the mechanical pulverizer is 30 to 60 ° C, more preferably 35 to 55 ° C. It is important to fine tune the minimum spacing. If it is below this temperature range, it is not sufficiently pulverized or the toner surface is not sufficiently cross-linked, so the electrostatic offset resistance decreases due to the increase in the amount of overcharged components accompanying the broadening of the charge distribution. In addition, there is a case where the durable developability is lowered as the wear resistance is lowered. On the other hand, if it exceeds this temperature range, it may be excessively pulverized at the time of pulverization, the resin melts due to heat, and the abundance of the layered compound on the toner surface becomes non-uniform, resulting in poor charging properties. It tends to be uniform and tends to cause a decrease in density and electrostatic offset during durability.

  Furthermore, it is also preferable to use a sieving device used for sieving coarse particles and the like, and examples of the sieving device include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sheave, Gyroshifter (Tokuju Kosakusha); Dalton Co.); Soniclean (Shinto Kogyo Co., Ltd.); Turbo Screener (Turbo Kogyo Co., Ltd.); Micro Shifter (Ogino Sangyo Co., Ltd.);

  The toner of the present invention preferably has a weight average particle diameter of 3 to 9 μm from the viewpoint of image density and resolution.

  The colorant contained in the toner of the present invention is preferable because the magnetic powder has an action of promoting dispersibility. This dispersibility promoting action is presumed to be because Si and Al interact with the magnetic powder. When magnetic powder is contained, it is preferable to use the following magnetic materials for reasons such as chargeability, dispersibility, and copy density uniformity.

Examples of the magnetic material include magnetic iron oxides including iron oxides such as magnetite, maghemite and ferrite, and other metal oxides; metals such as Fe, Co and Ni, or these metals and Al, Co, Pb, Examples thereof include alloys with metals such as Mg, Ni, Sn, Zn, Sb, Be, Bf, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures thereof. Conventionally, triiron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), iron yttrium oxide (Y ₃ Fe ₅ O ₁₂ ), cadmium iron oxide (Cd ₃ Fe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), iron oxide copper (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ) , Iron neodymium (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron Examples thereof include powder (Fe), cobalt powder (Co), and nickel powder (Ni). The above-described magnetic materials can be used alone or in combination of two or more. A particularly suitable magnetic material is a fine powder of iron tetroxide or γ-iron sesquioxide.

These magnetic powders have a SEM ferret diameter of 0.05 to 2 μm, a magnetic property of 79 to 58 kA / m applied, a saturation magnetization of 50 to ²⁰⁰ Am ² / kg (preferably 50 to 100 Am ² / kg), and a residual magnetization of 2 Those of ˜20 Am ² / kg are preferred.

  The magnetic powder is preferably contained in an amount of 30 to 150 parts by mass with respect to 100 parts by mass of the binder resin. When the magnetic powder is less than 30 parts by mass, the dispersibility-promoting action is insufficient, so that the dispersibility of the layered compound tends to decrease, and a concentration decrease and electrostatic offset are likely to occur. When the magnetic powder is contained in an amount of more than 150 parts by mass, the magnetically agglomerated magnetic powder inhibits the dispersibility of the layered compound, so that the concentration is reduced and electrostatic offset is likely to occur.

  The toner of the present invention can also be used as a non-magnetic toner, and in this case, any appropriate pigment or dye can be used as the colorant.

  In this case, for example, as a dye, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic green 6 etc. are mentioned. As pigments, yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartra gin lake, red mouth yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G , Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Bitumen, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Chrome Oxide, Pigment Green B, Malachite Green Lake, § Lee Naru yellow green G and the like.

  When the toner of the present invention is used as a full-color image forming toner, the following colorant can be used. Examples of the color pigment for magenta include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Although the magenta pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full color image to improve the sharpness by using a dye and a pigment together. In that case, as a magenta dye, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. are mentioned.

  Further, examples of the color pigment for cyan include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having the following structure.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 35, 73, 83, C.I. I. Examples include bat yellow 1, 3, 20 and the like.

  When used as a non-magnetic toner, the colorant may be contained in an amount of 0.1 to 60 parts by mass, more preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the binder resin.

  Examples of the binder resin of the toner of the present invention include polyester resins, styrene / acrylic resins, epoxy resins, styrene / butadiene resins, polyurethane resins, and the like, but are not particularly limited, and conventionally known resins can be used. Of these, polyester resins and styrene / acrylic resins are particularly preferable.

  Two or more of the above resins may be used in combination. In the present invention, the polyester resin component is contained in an amount of 50% by mass or more, and the reaction product of the polyester resin component and the vinyl resin component is used. It is preferable to use a resin containing a certain hybrid resin component because the dispersibility of the layered compound and the colorant is good, and the durability stability and electrostatic offset resistance are excellent.

  The following are mentioned as a monomer of the polyester resin used for this invention.

  As alcohol components, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Examples include diol, neopentyl glycol, 2-ethyl 1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the formula (a), and diols represented by the following formula (a).

  Divalent carboxylic acids containing 50 mol% or more of the total acid components include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; succinic acid, adipic acid, sebacic acid, and azelain. Alkyl dicarboxylic acids such as acids or anhydrides thereof, and succinic acid or anhydrides further substituted with an alkyl group having 6 to 18 carbon atoms: unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or the like; The anhydride etc. are mentioned.

  In addition, glycerin, pentaerythritol, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ethers of novolak-type phenol resins; polyvalent alcohols such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and anhydrides thereof Examples thereof include carboxylic acids.

  Moreover, what has the crosslinked structure bridge | crosslinked by the polyhydric carboxylic acid more than trivalence or its anhydride, or the polyhydric alcohol more than trivalence is preferable. Examples of the trivalent or higher polyvalent carboxylic acid or anhydride thereof include 1,2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, and These acid anhydrides or lower alkyl esters are mentioned, and examples of the trihydric or higher polyhydric alcohol include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol, etc. Is 1,2,4-benzenetricarboxylic acid and its anhydride.

  The following are mentioned as a vinyl-type monomer for producing | generating a styrene / acrylic-type resin.

  Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene Styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride Such as vinylidene chloride, vinyl bromide, vinyl fluoride Vinyl esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacrylic acid Α-methylene aliphatic monocarboxylic acid esters such as dodecyl, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate: methyl acrylate, ethyl acrylate, propyl acrylate , N-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic Acrylic esters such as phenyl oxalate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether: Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isoprohenyl ketone; N-vinyl pyrrole, N- N-vinyl compounds such as vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, cytofuconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester half ester of unsaturated base acid; dimethyl maleic acid, dimethyl fumaric acid unsaturated base acid ester; acrylic acid, methacrylate Α, β-unsaturated acid anhydrides such as acids, crotonic acid and cinnamic acid; anhydrides of the α, β-unsaturated acids and lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acids Examples thereof include monomers having a carboxyl group such as anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxylpropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1 -Methylhexyl) monomers having a hydroxyl group such as styrene.

  Moreover, the polymer bridge | crosslinked with the crosslinkable monomer which is illustrated below may be sufficient as needed.

  Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, and those obtained by replacing acrylate of the above compound with methacrylate: linked with an alkyl chain containing an ether bond. Examples of the diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol # 400 diacrylate. Acrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and the above compounds in which the acrylate is replaced by methacrylate; diacrylate compounds linked by chains containing aromatic groups and ether bonds Examples include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and the like Examples of the polyester-type diacryl derivatives include, for example, trade name MANDA (Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional cross-linking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and those obtained by replacing acrylate of the above compounds with methacrylate; And allyl cyanurate and triallyl trimellitate.

  Examples of the polymerization initiator used in producing the vinyl copolymer of the present invention include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4dimethyl). Valeronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisoptylate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl -4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclo Ketone peroxides such as xanone peroxide, 2,2'-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydro Peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide -Oxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, Acetylcyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy Laurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexano Et, di-t-butyl peroxyhex Hydro terephthalate, di -t- butyl peroxy azelate and the like.

  When the binder resin of the present invention contains a polyester resin component of 50% by mass or more and contains a hybrid resin component that is a reaction product of a polyester resin component and a vinyl resin component, It is preferable that the vinyl-based copolymer component and / or the polyester resin component contain a monomer component capable of reacting with both resin components. Examples of the monomer constituting the polyester resin component that can react with the vinyl copolymer include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method for obtaining a reaction product of a vinyl copolymer and a polyester resin, a polyester containing an unsaturated bond capable of reacting with the vinyl copolymer mentioned above is dissolved, and a vinyl monomer is dropped and polymerized there. A method obtained by reacting is preferred. Among these, as a monomer capable of reacting with a polyester resin and a vinyl copolymer, it is preferable that fumaric acid is contained in the total acid component in an amount of 0.1 to 10 mol% because the dispersibility of the layered compound of the present invention is improved. . If it is less than 0.1 mol%, the resin hybridization rate decreases, the dispersibility of the layered compound decreases, the durability developability and the electrostatic offset resistance deteriorate, and it is easily affected by the environment. If it exceeds 10 mol%, the dispersibility of the layered compound is lowered, and the durability and electrostatic offset resistance tend to deteriorate.

  In addition, when the acid value of the resin is 1 to 15 mgKOH / g, the dispersibility of the layered compound in the resin is excellent, and there are few monomer components remaining at the time of resin production, storage stability, durable developability, and electrostatic offset resistance. Is preferable. When the hydroxyl value of the resin is 10 to 50 mg KOH / g, the dispersibility increases due to its excellent affinity with the layered compound, and the monomer component in the resin can be reduced, storage stability and durable developability, Since it is excellent in electrostatic offset resistance, it is preferable.

  In the present invention, two types of resins having different softening points from the above components may be mixed and used.

  Further, the toner of the present invention may contain one or more kinds of waxes as a release agent as required.

  Examples of the wax include aliphatic hydrocarbon waxes such as low molecular polyethylene, low molecular polypropylene, microcrystalline wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; Block copolymers of waxes; waxes based on fatty acid esters such as carnauba wax, sazol wax and montanic acid ester wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax Can be mentioned. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as prundic acid, eleostearic acid, and valinal acid. Saturated alcohols such as stearic alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, or long chain alkyl alcohols having a long chain alkyl group; polyhydric alcohols such as sorbitol: stear Fatty acid metal salts such as calcium phosphate, calcium laurate, zinc stearate, magnesium stearate (generally called metal soap); vinyl monomers such as styrene and acrylic acid are used in aliphatic hydrocarbon waxes Partial esters of such fatty acids with polyhydric alcohols behenic acid monoglyceride; obtained by grafting waxes and methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oil and the like.

  In the toner of the present invention, a charge control agent can be used as necessary in order to further stabilize the charge amount. Since the layered compound used in the present invention is negatively chargeable, the charge control agent used in combination is preferably nonchargeable. For example, organometallic complexes and chelate compounds are effective. Examples thereof include monoazo metal complexes; acetylacetone metal complexes; aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid metal complexes and their metal salts, anhydrides, esters, and the like. And phenol derivatives such as bisphenol.

  For the purpose of controlling the charge amount of the toner, a positively chargeable charge control agent can also be used. For example, modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs of phosphonium salts thereof. Onium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide) Metal salts of higher fatty acids; diorganotin oxides such as dibutyl tin oxide, dioctyl tin oxide, dicyclohexyl tin oxide; dibutyl tin borate, dioctyl tin borate, dicyclohexane Such diorgano tin borate such Rusuzuboreto; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used.

  Moreover, charge control resin can also be used and can also be used together with the above-mentioned charge control agent.

  The toner of the present invention is preferably a negatively chargeable toner because the layered compound has a high negative chargeability.

Silica fine particles are mentioned as an external additive suitably used for the toner of the present invention. Examples of the silica fine particles include fine powder silica such as wet process silica and dry process silica, and treated silica obtained by surface-treating these silicas with a silane coupling agent, a titanium coupling agent, silicone oil, or the like. Further, preferred silica fine particles include what is called dry process silica or fumed silica produced by vapor phase oxidation of a silicon halogen compound, and are produced by a conventionally known technique. For example, it utilizes a thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is represented by the following general formula (3).
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl (3)

  In this production process, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. Include. The particle diameter is preferably in the range of 0.001 to 2 μm as an arithmetic average diameter, and particularly preferably silica fine powder in the range of 0.002 to 0.2 μm is used.

  Furthermore, it is preferable to use treated silica fine particles obtained by hydrophobizing silica fine particles produced by vapor phase oxidation of the silicon halide compound.

  As a hydrophobizing method, it is applied by chemical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine particles. As a preferred method, silica fine particles produced by vapor phase oxidation of a silicon halogen compound are treated with an organosilicon compound. Such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane. , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, 1-hexamethyldisiloxane, 1,3-divinyltetramethyldisilo Xan, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit It is done. These are used alone or in a mixture of two or more.

  The silica fine particles may be treated with a silicone oil, or may be treated in combination with the hydrophobic treatment.

Preferred silicone oils are those having a viscosity at 25 ° C. of 30 to 1000 mm ² / s (centistokes), such as dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil. Fluorine-modified silicone oil and the like are preferable.

  As a method for treating silicone oil, for example, a method in which silica fine particles treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; Or a method of dissolving or dispersing silicone oil in a suitable solvent and then adding and mixing silica fine particles to remove the solvent. More preferably, the silicone oil-treated silica is heated to 200 ° C. or higher (more preferably 250 ° C. or higher) in an inert gas after the silicone oil is treated to stabilize the surface coating.

  Aminopropyltrimethoxysilane having nitrogen atom, aminopropyltriethoxycin, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, monobutylaminopropyltrimethoxy Silanes such as silane, dioctylaminopropyldimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ-propylbenzylamine A coupling agent may be used alone or in combination. A preferred silane coupling agent is hexamethyldisilazane (HMDS).

  The external additive is preferably used in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner of the present invention.

  Examples of such external additives include, but are not limited to, charging aids, conductivity-imparting agents, fluidity-imparting agents, anti-caking agents, mold release agents, lubricants, abrasives, etc. Examples include fine particles. More specifically, for example, a lubricant such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride, preferably polyvinylidene fluoride is preferable. Alternatively, an abrasive such as cerium oxide, silicon carbide, strontium titanate, etc., among which strontium titanate is preferable. Alternatively, a fluidity-imparting agent such as aluminum oxide, particularly a hydrophobic one is preferably mentioned. Alternatively, an anti-caking agent, a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide, and tin oxide, or fine particles with reverse polarity can be used.

  Next, a method for measuring various physical property data according to the present invention is shown below.

(1) Measurement of toner particle size distribution A Coulter counter Multisizer II (manufactured by Coulter, Inc.) is used as a measuring device. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement apparatus is used to form toner particles having a particle diameter of 2.00 to 40.30 μm using a 100 μm aperture as an aperture. Volume and number Measure for each channel to calculate the toner volume distribution and number distribution. Then, the weight average particle size (D4) of the toner particles based on the weight obtained from the volume distribution of the toner particles (with the median value of each channel as a representative value for each channel) is obtained.

  As the channel, 1.59 to 2.00; 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm in the case of toner measurement. 5.04 to 6.35 μm; 6.35 to 8.00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; Use 12 channels of 20-25.40 μm.

(2) SEM Ferret Diameter of Magnetic Material The SEM ferret diameter of the magnetic material according to the present invention is calculated by taking a photograph of a scanning electron microscope (30000 times).

(3) Magnetic Properties of Magnetic Material The saturation magnetization σs and residual magnetization σr of the magnetic material according to the present invention are measured with a vibrating sample magnetometer VSM-P7 (manufactured by Toei Kogyo Co., Ltd.) with 795.8 kA / m). .

(4) Measurement of glass transition temperature of binder resin Measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by Perkin Elmer).

  The measurement sample is precisely weighed in an amount of 2 to 10 mg, preferably 5 mg. This is put into an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at a temperature rise rate of 10 ° C./min. In this temperature raising process, an endothermic peak of the main peak of the DSC curve in the range of 40 to 100 ° C. is obtained. The intersection of the midpoint of the baseline before and after the endothermic main peak and the differential heat curve is defined as the glass transition temperature in the present invention.

(5) Measurement of particle size distribution of layered compound and silica In the present invention, the median diameter of the layered compound, the standard deviation of the arithmetic mean diameter, the particle size distribution, and the arithmetic mean diameter of the silica are measured by a laser diffraction scattering type particle size distribution measuring device (manufactured by LA-920 "). For the measurement, a cell type sample cell was used. First, ion exchange water is put into the cell, and zero point adjustment is performed. Thereafter, 10 ml of ion-exchanged water is added to the vial, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant, and 1 to 20 mg of a measurement sample is further added. Thereafter, the sample is suspended, the vial is placed on an ultrasonic disperser, and the dispersion treatment is performed for about 3 minutes. The aqueous solution after the dispersion treatment was put into a sample cell so that the light transmittance was 80 to 90%, and measured. The particle diameter was a value calculated on a volume basis.

(6) Calculation of layered compound matrix / organic weight ratio (thermogravimetric analysis)
The calculation of the weight ratio of the layered compound base / organic matter in the present invention is determined from the reduced weight ratio obtained by thermogravimetric analysis. The apparatus used was TGA-2950, and the temperature was raised in two stages. The first stage is heated to 750 ° C. at a temperature increase rate of 25 ° C./min in a nitrogen atmosphere, and the second stage is heated to 900 ° C. at a temperature increase rate of 750 ° C./min after reducing the weight. Minutes were the organic matter ratio.

(7) Calculation of interlayer distance of layered compound (X-ray diffractometer)
The interlayer distance of the layered compound can be determined from the diffraction angle peak angle by performing a 2θ scan of the diffraction image using an X-ray diffractometer.

  The layered compound according to the present invention is spread on an aluminum sample holder so that the measurement surfaces are evenly aligned, and the interlayer distance of the layered mineral is measured by 2θ / θ scanning method using an X-ray diffractometer (TTR-2, manufactured by Rigaku Corporation). And measured up to θ = 10 °. The X-ray diffraction measurement was performed using an X-ray output of 50 kV and 300 mA CuKα rays, a divergence slit of 0.2 mm, a divergence longitudinal limit slit of 10.00 mm, a scattering slit opened, a light receiving slit of 0.15 mm, and an incident monochromator used. It was.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

(Production Example 1 of layered compound)
34.2 parts by mass of dimethyl distearyl ammonium chloride and 3.8 parts by mass of methyl tristearyl ammonium chloride were dissolved in 200 parts by mass of chloroform. To this, 62 parts by mass of sodium salt of layered silicic acid having an Fe content of 1.5% by mass was added and stirred for 1 hour, followed by filtration. Further, after repeatedly washing with distilled water, it was sufficiently dried. Thereafter, pulverization and classification were performed to obtain a layered compound 1. The particle size and composition are shown in Table 1.

(Production Examples 2 and 3 of the layered compound)
By synthesizing in the same manner as in Production Example 1, and adjusting in the pulverization and classification steps, a layered compound 2 having a median diameter of 2.5 μm and a layered compound 3 having a median diameter of 2.0 μm were obtained. The particle size and composition are shown in Table 1.

(Production Examples 4 and 5 of the layered compound)
A layered compound 4 was obtained by synthesizing in the same manner as in Production Example 1 and adjusting in the classification step. The particle size and composition are shown in Table 1.

(Production Example 5 of layered compound)
In Production Example 1, the same procedure was carried out using 30.4 parts by mass of dimethyldistearylammonium chloride and 7.6 parts by mass of methyltristearylammonium chloride to obtain layered compound 5. The particle size and composition are shown in Table 1.

(Production Example 6 of layered compound)
In Production Example 1, the same operation was carried out using 38 parts by mass of dimethyldistearylammonium chloride as the reagent to be used, and the layered compound 6 was obtained. The particle size and composition are shown in Table 1.

(Production Example 7 of layered compound)
In Production Example 1, the same operation was performed using 38 parts by mass of trimethyl monostearyl ammonium chloride as the reagent to be used, and thus a layered compound 7 was obtained. The particle size and composition are shown in Table 1.

(Production Example 8 of layered compound)
In Production Example 1, the same operation was carried out by using 35 parts by mass of trimethylmonostearylammonium chloride as the reagent to be used and 65 parts by mass of the sodium salt of layered silicic acid to be used, thereby obtaining layered compound 5. The particle size and composition are shown in Table 1.

(Production Example 9 of layered compound)
In Production Example 1, the same operation was carried out using 30 parts by mass of trimethylmonostearylammonium chloride as the reagent to be used and 70 parts by mass of the sodium salt of layered silicic acid to be used, thereby obtaining layered compound 9. The particle size and composition are shown in Table 1.

(Production Example 10 of layered compound)
In Production Example 1, the same operation was carried out using 45 parts by mass of the reagent used as trimethylmonostearylammonium chloride and 55 parts by mass of the sodium salt of layered silicic acid used to obtain a layered compound 10. The particle size and composition are shown in Table 1.

(Production Example 11 of layered compound)
In Production Example 1, the same operation was carried out using 38 parts by mass of tetraethylammonium chloride as the reagent to be used, whereby a layered compound 11 was obtained. The particle size and composition are shown in Table 1.

(Production Example 12 of layered compound)
Layered silicic acid sodium salt having an Fe content of 1.5 mass% was pulverized and classified to obtain layered compound 12. The particle size and composition are shown in Table 1.

(Production Example 13 of layered compound)
Layered silicic acid sodium salt having an Fe content of 0.1% by mass was pulverized and classified to obtain layered compound 13. The particle size and composition are shown in Table 1.

(Production Example 14 of layered compound)
A layered compound 14 was obtained by pulverizing and classifying sodium salt of layered silicic acid having an Fe content of 5.0% by mass. The particle size and composition are shown in Table 1.

(Production Examples 15 to 19 of the layered compound)
In the manufacture example 12 of a layered compound, adjustment in a grinding | pulverization and a classification process was performed, and the layered compounds 15-19 were obtained. The particle size and composition are shown in Table 1.

(Production Example 20 of layered compound)
The same operation as in Production Example 6 was conducted except that pulverization and classification were omitted, and a layered compound 20 was obtained. The particle size and composition are shown in Table 1.

(Binder Resin Production Example 1)
Terephthalic acid 19mol%
Isophthalic acid 30mol%
Fumaric acid 1mol%
50 mol% of bisphenol derivative represented by the formula (a)
(Propylene oxide 2.5 mol adduct)
The polyester monomer was charged into a four-necked flask, and a polycondensation reaction was performed by heating to 230 ° C. in a nitrogen atmosphere with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device. . After completion of the reaction, it was taken out from the container, cooled and pulverized to obtain a polyester resin. This polyester resin was put again into the flask, and when heated to 140 ° C. and dissolved, a vinyl resin monomer (styrene: 78 mol%, butyl acrylate: 20 mol%, monobutyl maleate: 2 mol%), dibenzoyl as a polymerization initiator A mixture of peroxides was dropped from a dropping funnel over 8 hours. The reaction was carried out by aging for 4 hours while maintaining the temperature at 140 ° C. After completion, the reaction product was taken out from the container, cooled and pulverized to obtain a binder resin 1. Table 2 shows the resin monomer composition.

(Binder Resin Production Examples 2 to 4)
Except having changed the polyester monomer like Table 2, operation similar to manufacture example 1 was performed and binder resin 2-4 was obtained.

(Binder Resin Production Example 5)
A binder resin 5 was obtained in the same manner as in Production Example 1 except that the polymerization reaction was performed until the acid value of the resin reached 1 mgKOH / g.

(Binder Resin Production Example 6)
In Production Example 1, the same operation was carried out except that the polymerization reaction was terminated when the acid value of the resin reached 15 mgKOH / g, whereby a binder resin 6 was obtained.

(Binder Resin Production Example 7)
Terephthalic acid 19mol%
Isophthalic acid 30mol%
Fumaric acid 1mol%
50 mol% of bisphenol derivative represented by the formula (a)
(Propylene oxide 2.5 mol adduct)
The polyester monomer was charged into a four-necked flask, and a polycondensation reaction was performed by heating to 230 ° C. in a nitrogen atmosphere with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device. . After completion of the reaction, it was taken out from the container, cooled and pulverized to obtain a binder resin 7.

(Binder Resin Production Examples 8-9)
Except having changed the resin monomer like Table 2, operation similar to manufacture example 7 was performed and the binder resins 8-9 were obtained.

<Example 1>
Binder resin 1 100 parts by weight magnetic body 95 mass parts (SEM Feret's ^{diameter: 0.19μm, σs: 83.6Am 2 /kg,σr:6.5Am} 2 / kg)
Layered compound 1 2 parts by weight Polyethylene wax (melting point 105 ° C.) 5 parts by weight (Sazol, C105)
The above raw materials are mixed with a Henschel mixer for 3 minutes, melt-kneaded with a twin screw extruder PCM-30 heated to 160 ° C, cooled with a cooling belt (cooling water 15 ° C), and then the mixture is coarsely pulverized with a hammer mill. did. The toner temperature immediately after the discharge port during melt-kneading was 155 ° C. The coarsely pulverized product was finely pulverized by adjusting the exhaust temperature to 45 ° C. in a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified with an air classifier to obtain a toner base.

To 100 parts by mass of this toner base, 1.35 parts by mass of hydrophobic dry silica (BET 180 m ^{2 /} g) was externally added with a Henschel mixer to obtain toner 1 having a weight average diameter (D4) of 6.8 μm.

  Using the toner 1, the following evaluations 1 and 2 were performed. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

Evaluation 1. Image density evaluation (Table 4)
The image density tends to decrease due to insufficient charge when the amount of moisture in the air is large. In particular, in the case of outputting an image such as a solid image in which the developer is rapidly changed, since the charging start-up time is short, it is difficult to obtain a uniform and sufficient charge amount, and the image density is likely to decrease. Therefore, in the present invention, in order to evaluate the performance under severe conditions, an evaluation method in which a solid black image is continuously drawn under a high temperature and high humidity environment is adopted.

  800 g of toner 1 is weighed, and a commercially available laser beam printer LaserJet 4300n (manufactured by Hewlett Packard) is modified to change the thickness of the elastic blade in contact with the sleeve to 30%, thereby changing the contact pressure of the blade to 29 .4N / m (30g weight / cm) to 49N / m (50g weight / cm), process speed 350mm / sec, 4300n CRG and high temperature and high humidity environment (32.5 ° C, 82.5% And H / H) for 12 hours. After that, the toner 1 was put into the developing unit and installed at 4300n, and a solid black image was printed at 10,000 A4. The obtained solid black image was sampled at the beginning and last 10 of the endurance, and the density of 6 points was measured with a reflection densitometer RD918 (manufactured by Macbeth). The density measurement position was set at the center of each of six rectangles formed by dividing the long side of A4 paper into three and the short side into two. The average value in the obtained data of 60 points was recorded.

Evaluation 2. Electrostatic offset test (Table 5)
The electrostatic offset is a phenomenon that occurs due to toner electrostatically adhering to the fixing roller side when the paper on which the toner is placed passes through the fixing device. Therefore, the evaluation under the environment where excessive charging is promoted such as a low humidity environment and the situation where the fixing roller is charged after continuous paper passing is the strictest against electrostatic offset. In addition, when the paper to be passed is coated on the surface, both the toner and the fixing roller are more easily charged than normal paper such as recycled paper, and thus electrostatic offset is likely to occur. In consideration of these points, the toner of the present invention was evaluated.

1) Recycled paper evaluation A printer in which 800 g of toner 1 is weighed and a laser beam printer LaserJet 9050n (manufactured by Hewlett Packard) is modified so that the process speed can be changed stepwise to 300, 350, 400, and 550 mm / sec. The temperature and humidity were adjusted for 12 hours in a high temperature and low humidity environment (32.5 ° C., 5%, hereinafter H / L) together with CRG for 9050n. Thereafter, the toner 1 was put into the CRG, installed at 9050n, and a solid white image was continuously passed through A4 paper (recycled paper EW100 manufactured by Canon Inc.) 1000 sheets. Thereafter, 100 images were continuously drawn using an electrostatic offset test chart in which the first half of the image was solid black and the second half was white, and the electrostatic offset resistance was visually evaluated.

2) Evaluation of coated paper Using CRG after evaluation of recycled paper, the paper was changed to coated paper (Image Coat Gloss 100, manufactured by Canon Inc.), and 1000 solid white images were continuously passed again. Thereafter, 100 continuous images were drawn using the same electrostatic offset test chart as that for recycled paper evaluation, and the electrostatic offset resistance was visually evaluated.

In addition, the evaluation criteria of the electrostatic offset resistance in 1) and 2) were determined as follows.
A It is not seen at all.
B Can be seen faintly on a white background.
C Can be seen in a small part on the white background.
D It is faintly seen in a slightly wide area on the white background.
E Faint over a wide area of white background.
F Appears clearly in a wide area of white background.
G Remarkably appears on the white background.

Evaluation 3. Preservability evaluation (Table 4)
About 10 g of toner was put in a 100 cc polycup and allowed to stand at 60 ° C. for one week, and then the influence on the toner was visually evaluated.
A: Very good (no change)
B: About 1 to 10 aggregates are seen, but are easily loosened.
C: About 11 to 20 aggregates are seen, but are easily loosened.
D: Although about 11 to 20 aggregates are seen, they are easily loosened.
E: Many agglomerates are observed, and about 11 to 20 are found that are not easily loosened.
F: Although it becomes the aggregate on the whole, when all are lightly pressed with a finger, it will be crushed.
G: Although it is an aggregate as a whole, there are some which are hard to be crushed by pressing with a finger.
H: Making a cake.

<Examples 2 to 9>
The same operations as in Example 1 were carried out except that binder resins 2 to 9 were used, and toners 2 to 9 having a weight average diameter (D4) of 6.8 μm were obtained. The same evaluation as in Example 1 was performed using toners 2 to 9. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Examples 10 to 12>
In Example 1, the same operation was performed except that the binder resin 9 was used and the layered compounds 2 to 4 were used, and toners 10 to 12 having a weight average diameter (D4) of 6.8 μm were obtained. The same evaluation as in Example 1 was performed using toners 10 to 12. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Examples 13 to 27>
A toner 13 to 27 having a weight average diameter (D4) of 6.8 μm was obtained in Example 1 except that the binder resin 7 was used and the layered compounds 5 to 19 were used. The same evaluation as in Example 1 was performed using toners 13 to 27. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Comparative Example 1>
The same operation as in Example 1 was performed except that the binder resin 7 was used and the layered compound 20 was used to obtain a comparative toner 1 having a weight average diameter (D4) of 6.8 μm. The same evaluation as in Example 1 was performed using the comparative toner 1. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Comparative example 2>
The same operation was performed as in Example 1 except that the binder resin 7 was used, 150 parts by mass of the magnetic powder, and the layered compound 20 were used to obtain a comparative toner 2 having a weight average diameter (D4) of 6.8 μm. . The same evaluation as in Example 1 was performed using the comparative toner 2. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Comparative Example 3>
A toner 4 for comparison having a weight average diameter (D4) of 6.8 μm was obtained in the same manner as in Example 1 except that the binder resin 7 was used, 30 parts by mass of the magnetic powder, and the layered compound 20 were used. . The same evaluation as in Example 1 was performed using the comparative toner 3. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Comparative example 4>
In Example 1, the same operation was performed except that the binder resin 7 was used, the layered compound 20 was used, and the toner temperature at the time of melt kneading was adjusted to 190 ° C., and the weight average diameter (D4) was 6.8 μm for comparison. Toner 4 was obtained. The same evaluation as in Example 1 was performed using the comparative toner 4. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Comparative Example 5>
In Example 1, the same operation was performed except that the binder resin 7 was used, the layered compound 20 was used, and the toner temperature at the time of melt kneading was adjusted to 140 ° C., and the weight average diameter (D4) was 6.8 μm for comparison. Toner 5 was obtained. The same evaluation as in Example 1 was performed using the comparative toner 5. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Comparative Example 6>
In Example 1, the same operation was performed except that the binder resin 7 was used, the layered compound 20 was used, and the discharge temperature at the time of fine pulverization was adjusted to 55 ° C., and the weight average diameter (D4) was 6.8 μm for comparison. Toner 6 was obtained. The same evaluation as in Example 1 was performed using the comparative toner 6. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

<Comparative Example 7>
In Example 1, the same operation was performed except that the binder resin 7 was used, the layered compound 20 was used, and the discharge temperature at the time of fine pulverization was adjusted to 35 ° C., and the weight average diameter (D4) was 6.8 μm for comparison. Toner 7 was obtained. The same evaluation as in Example 1 was performed using the comparative toner 7. The toner formulation is shown in Table 3, and the results are shown in Tables 4 and 5.

Claims (5)

In a toner containing at least a binder resin, a colorant, and a layered compound having Al and Si,
The toner is produced through at least the binder resin, the colorant, and the layered compound through at least a raw material mixing step, a melt-kneading step, a pulverizing step, and a classification step,
The standard deviation of the arithmetic mean diameter of the layered compound before the raw material mixing step is 2.0 or less, the median diameter is 4 μm or less, and the content of particles of 10 μm or more is 3% or less. Toner.   The toner according to claim 1, wherein the layered compound contains 0.1 to 5% by mass of Fe.   The toner according to claim 1, wherein the layered compound contains an organic substance, and the organic substance is a compound containing nitrogen.   4. The toner according to claim 1, wherein the layered compound contains an organic substance, and the organic substance contains a dimethyl distearyl ammonium salt.   The toner according to claim 1, wherein the toner contains 30 to 150 parts by mass of magnetic powder with respect to 100 parts by mass of the binder resin.